CN114835159A - Preparation method of reduced graphene oxide loaded lead oxide composite material for lead-carbon battery - Google Patents
Preparation method of reduced graphene oxide loaded lead oxide composite material for lead-carbon battery Download PDFInfo
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Abstract
The invention relates to the technical field of lead-carbon batteries, and aims to provide a preparation method of a reduced graphene oxide loaded lead oxide composite material for a lead-carbon battery. The method comprises the following steps: fully mixing the graphene oxide dispersion liquid with aniline and lead acetate solution, and then adding the mixture into a reaction kettle to perform hydrothermal reaction; separating the graphene/lead composite hydrogel in the reaction product, and washing with absolute ethyl alcohol and deionized water; then carrying out condensation treatment and freeze drying to obtain reduced graphene oxide/lead oxide composite material aerogel; and calcining the reduced graphene oxide/lead oxide composite aerogel under the protection of argon to obtain the reduced graphene oxide loaded lead oxide composite. The composite material can avoid the phenomena of graphene agglomeration and carbon floating in the material mixing process, and greatly improves the dispersion uniformity of the carbon material in the negative plate of the lead-carbon battery; the hydrogen evolution amount in the charging process of the battery can be reduced, and the shortening of the service life of the battery caused by the drying of the electrolyte is avoided.
Description
Technical Field
The invention relates to the technical field of lead-carbon batteries, in particular to a preparation method of a reduced graphene oxide loaded lead oxide composite material for a lead-carbon battery, and relates to a simple and efficient preparation method of a reduced graphene oxide/lead oxide composite material and application of the reduced graphene oxide/lead oxide composite material as a negative active additive in the lead-carbon battery.
Background
The lead-acid battery is a secondary battery with the largest market share and the widest application range in chemical batteries, has the comparative advantages of lower price, mature technology, excellent high and low temperature performance, stability, reliability, high safety, good resource recycling property and the like, and has obvious market competitive advantage. The lead-acid battery has the following disadvantages: low energy density and short cycle life.
Negative sulfation is a key factor for the deterioration of the performance of the traditional lead-acid storage battery, and a new lead-acid system needs to be developed. The lead-carbon battery is a capacitive lead-acid battery evolved from a traditional lead-acid battery, and the service life of the battery is prolonged by effectively inhibiting negative electrode sulfation by introducing a carbon material into a negative electrode of the lead-acid battery.
At present, different types of carbon materials such as activated carbon, carbon black, mesoporous carbon, carbon nanotubes, graphite, graphene oxide, graphene and the like have been introduced into the negative electrode of a lead-acid battery to improve the battery performance. The mechanism of action is summarized as follows: (a) the carbon material can increase the conductivity of the negative electrode active material by constructing a conductive network in the negative electrode active material; (b) the carbon material can promote the formation of easily dissolved small lead sulfate grains and inhibit the growth of the small lead sulfate grains, namely the steric hindrance effect; (c) the reduction potential of the lead on the surface of the carbon material is low, so that the carbon material can provide more active sites for reducing the lead sulfate into the spongy lead and limit the growth of lead sulfate crystals; (d) under high-rate charge and discharge, the carbon material can be used as an electroosmosis pump to promote the electrolyte solution to permeate into the negative active material; (e) the carbon with high specific surface area can play a capacitance characteristic in the negative active material and can play a role of a super capacitor; (f) some carbon materials contain impurities that can suppress the evolution of hydrogen gas and improve charging efficiency.
Graphene is a novel two-dimensional conductive material, and is composed of a single-layer carbon atom, and a basic structural unit of the graphene is a six-membered ring structure, so that the graphene has good chemical stability. The graphene has a high specific surface area, so that a large reaction interface can be provided, and the dispersibility of the surface nano material can be improved; the graphene has high conductivity, and is beneficial to the transfer of electronic charges in the electrochemical reaction process; the winding among the graphene sheet layers can provide a pore structure beneficial to electrolyte permeation and ion diffusion, so that the electrochemical performance of the lead-acid battery can be remarkably improved by using the conductive composite material constructed based on graphene as a negative electrode additive.
However, the density of the graphene material is low, the carbon floating effect can occur when the graphene material is added into negative lead paste, lead and carbon can be loosely combined, and the introduction of the graphene material can aggravate the problem of hydrogen evolution of the negative electrode, so that the electrolyte is dehydrated and dried, and therefore the graphene material needs to be subjected to composite modification; meanwhile, the graphene material is easy to aggregate and agglomerate, has a smooth and inert surface, and is not beneficial to compounding with other materials, so that effective functional treatment must be carried out on the graphene material.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides a preparation method of a reduced graphene oxide loaded lead oxide composite material for a lead-carbon battery.
In order to solve the technical problem, the solution of the invention is as follows:
the preparation method of the reduced graphene oxide loaded lead oxide composite material for the lead-carbon battery comprises the following steps:
(1) fully mixing the graphene oxide dispersion liquid with aniline and lead acetate solution, and then adding the mixture into a reaction kettle to perform hydrothermal reaction; in the reaction raw materials, the mass ratio of the graphene oxide to the aniline to the lead acetate is 1: 5-20: 6-10;
(2) separating the graphene/lead composite hydrogel in the reaction product, and washing with absolute ethyl alcohol and deionized water; then carrying out condensation treatment and freeze drying to obtain reduced graphene oxide/lead oxide composite material aerogel;
(3) and calcining the reduced graphene oxide/lead oxide composite aerogel under the protection of argon to obtain the reduced graphene oxide loaded lead oxide composite.
In a preferred embodiment of the present invention, in the step (1), before the hydrothermal reaction:
(1.1) adding lead acetate (Pb (CH) 3 COO) 2 ·3H 2 O) dissolving in deionized water to obtain a lead acetate solution;
(1.2) adding aniline into the graphene oxide dispersion liquid, magnetically stirring for 2 hours, and adding an alkali solution to adjust the pH value to 3-10; and adding a lead acetate solution into the mixture, continuously stirring the mixture for 2 hours, and using the obtained mixed solution for hydrothermal reaction.
As a preferred embodiment of the present invention, the alkali solution used is obtained by dissolving KOH in deionized water.
In a preferred embodiment of the present invention, the solvent of the graphene oxide dispersion is a mixed solvent of ethanol and water in a volume ratio of 1: 1.
As a preferable mode of the invention, the concentrations of the lead acetate solution, the alkali solution and the graphene oxide dispersion liquid are 100mg/mL, 1mol/L and 1mg/mL respectively.
In a preferable embodiment of the invention, in the step (1), the hydrothermal reaction is carried out at 180 ℃ for 12-36 hours.
In a preferable embodiment of the invention, in the step (2), the temperatures of the condensation treatment and the freeze drying are both-60 ℃; wherein the time for the condensation treatment was 12 hours, and the time for the freeze-drying was 24 hours.
In a preferred embodiment of the present invention, in the step (2), the freeze-drying is performed under vacuum.
In a preferable embodiment of the present invention, in the step (3), the calcination temperature is 450 ℃, and the calcination time is 2 hours; the heating rate in the calcination process is 5 ℃/min.
The invention further provides an application method of the reduced graphene oxide loaded lead oxide composite material, which is characterized in that the composite material is used as a negative electrode additive, is uniformly mixed with lead powder, acetylene black, barium sulfate, humic acid, sodium lignosulphonate, short fibers, deionized water and dilute sulfuric acid, is coated on a lead grid, and is solidified to obtain the negative electrode green plate of the lead-acid battery.
Description of the inventive principles:
in the existing process flow, in the process of introducing graphene into a negative electrode material of a lead-acid battery, a common treatment method is to mechanically mix the graphene material and micron-sized lead powder, but graphene lamellar layers are easy to agglomerate in the mixing process and are difficult to exert the characteristic of high conductivity, and because the density of the lead powder is not matched with that of the graphene, the graphene lamellar layers and the graphene lamellar layers are difficult to uniformly mix, so that the layering phenomenon is extremely generated in the use process, and the service life of the battery is influenced.
The invention breaks through the limitation of the solution idea and provides a brand-new preparation technology of the reduced graphene oxide/lead oxide composite material. The method comprises the following steps of (1) reducing graphene oxide, namely performing intercalation dispersion on graphite by adopting a chemical method, and modifying oxygen-containing functional groups on the surface of the graphite to form graphite oxide or graphene oxide; and then, reducing and eliminating the functional groups on the surface by using a strong reducing agent to obtain the reduced graphene oxide. The graphene prepared by the method has more surface defects, contains more oxygen-containing functional groups, is easy to carry out surface modification, can realize large-scale production of the graphene, and is more suitable for industrial application than the method for stripping the graphene by a physical method.
According to the reduced graphene oxide/lead oxide nano composite material prepared by the invention, lead oxide particles are uniformly loaded between the reduced graphene oxide lamella layers, the diameter size is controllably adjusted between 20-500 nanometers, the agglomeration of graphene is avoided, and the uniform dispersion of graphene and lead compounds is realized; the density of the carbon material is improved, the phenomenon of carbon floating in the mixing process of the graphene and the lead negative electrode material is reduced, and the charge acceptance of the lead-acid battery and the HRPSoC cycle life can be remarkably improved; meanwhile, nitrogen doping and compounding of lead oxide and graphene can effectively improve the hydrogen evolution overpotential of the additive and solve the problem of water loss of the lead-carbon battery.
Compared with the prior art, the invention has the beneficial effects that:
1. the reduced graphene oxide/lead oxide composite material prepared by the invention can avoid the phenomena of graphene agglomeration and carbon floating in the material mixing process, and greatly improves the dispersion uniformity of the carbon material in the negative plate of the lead-carbon battery.
2. Because lead has higher hydrogen evolution overpotential, the reduced graphene oxide/lead oxide composite material prepared by the invention has higher hydrogen evolution overpotential than a single graphene material, so that the hydrogen evolution amount in the charging process of a battery can be reduced, and the service life of the battery is prevented from being shortened due to the dryness of electrolyte.
3. The reduced graphene oxide/lead oxide composite material prepared by the invention is of a porous lamellar structure, and graphene has a current buffering effect on the polar plate, so that the conductivity of the polar plate is improved, and the conversion rate and the utilization rate of active substances in the polar plate are greatly improved.
4. The particle size of the reduced graphene oxide/lead oxide composite material prepared by the invention can be controllably adjusted in a larger range of 50nm-300nm by adjusting parameters in the technical scheme, and because amino or imino functional groups in aniline molecules can effectively adsorb lead ions through electrostatic action and coordination complexing action, and nitrogen-containing functional groups of the composite material have reducibility and can be subjected to redox adsorption with lead ions with stronger oxidizability, the adsorption capacity of graphene oxide sheet layers on the lead ions is enhanced, the active sites of the composite material are increased, and the performance characteristics of the composite material are enriched.
5. The charging and discharging performance and the cycle capacity of the battery prepared by adding the reduced graphene oxide/lead oxide composite material prepared by the invention serving as an additive into a negative electrode material of a lead-acid battery are obviously improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a reduced graphene oxide material prepared without adding aniline and lead acetate.
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a reduced graphene oxide material prepared by a hydrothermal method without adding lead acetate.
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of a reduced graphene oxide material prepared by a hydrothermal method without adding aniline.
FIG. 4 is a Scanning Electron Microscope (SEM) photograph of an A1 sample prepared in example 1 of the present invention.
FIG. 5 is a Transmission Electron Microscope (TEM) photograph of an A1 sample prepared in example 1 of the present invention.
Fig. 6 is a schematic diagram showing the cycle life comparison of the high rate partial charge condition (HRPSoC) measured after the negative green plates prepared in examples 1 to 6, the blank comparative example, and the common comparative example are assembled into a flooded battery.
Fig. 7 is a schematic diagram showing the comparison of specific capacities measured after negative green plates prepared in examples 1 to 6, blank comparative example and conventional comparative example were assembled into a flooded battery.
FIG. 8 is a comparative graph showing hydrogen evolution performance of the negative electrode green sheets obtained in example 1, the blank comparative example and the conventional comparative example.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described below with reference to the accompanying drawings and embodiments.
Example 1
(1) Weighing 100mg of lead acetate, and dissolving the lead acetate in 1mL of deionized water to obtain a 100mg/mL lead acetate solution; 56g of KOH powder was weighed into a 1L volumetric flask to prepare a 1mol/L KOH alkaline solution.
(2) Taking 10 ml of 1mg/ml graphene oxide dispersion liquid, wherein the solvent of the graphene oxide dispersion liquid is a mixed solvent of ethanol and water in a volume ratio of 1: 1. Weighing 100mg of aniline, adding the aniline into the graphene oxide dispersion liquid, magnetically stirring for 2 hours, dropwise adding 1mol/L KOH alkali solution, adding the solution into the mixed solution, stirring, adjusting the pH to 7, weighing 0.8mL of 100mg/mL lead acetate solution, and fully stirring for 2 hours. The resulting dispersion was transferred to a 25ml Teflon reactor and allowed to react at 180 ℃ for 24 hours. And after the reaction kettle is cooled to room temperature, separating the graphene composite hydrogel obtained by the reaction through suction filtration, and washing with absolute ethyl alcohol and deionized water respectively.
(3) And (3) condensing the hydrogel obtained in the step (2) at-60 ℃ for 12 hours, and then, turning on a vacuum pump to freeze and dry for 24 hours to obtain the graphene composite aerogel.
(4) And (4) placing the graphene composite material aerogel obtained in the step (3) in a tubular furnace, continuously introducing argon, heating to 450 ℃ at the heating rate of 5 ℃/min, and calcining for 2h to decompose redundant organic structures in the composite material and completely convert lead into lead oxide. And after the calcination and sintering, continuously introducing argon until the temperature in the tube is reduced to room temperature, and finally obtaining the reduced graphene oxide/lead oxide composite material (marked as A-1).
(5) Using the graphene/lead oxide (A-1) (0.5 wt% relative to lead powder) obtained in the step (4) as a negative electrode additive, mixing with lead powder (100 wt%), acetylene black (0.2 wt%), barium sulfate (0.83 wt%), humic acid (0.46 wt%), sodium lignosulfonate (0.4 wt%), short fibers (0.052 wt%), deionized water (12.5 wt%) and dilute sulfuric acid (7.9 wt%, 1.40g cm) -3 ) And uniformly mixing, coating on a lead grid, and curing to obtain the negative green plate of the lead-acid battery.
Example 2
(1) Weighing 100mg of lead acetate, and dissolving the lead acetate in 1mL of deionized water to obtain a 100mg/mL lead acetate solution; 56g of KOH powder was weighed into a 1L volumetric flask to prepare a 1mol/L KOH alkaline solution.
(2) Taking 10 ml of 1mg/ml graphene oxide dispersion liquid, wherein the solvent of the graphene oxide dispersion liquid is a mixed solvent of ethanol and water in a volume ratio of 1: 1. Weighing 50mg of aniline, adding the aniline into the graphene oxide dispersion liquid, magnetically stirring for 2 hours, dropwise adding 1mol/L KOH alkali solution, adding the solution into the mixed solution, stirring, adjusting the pH to 7, weighing 0.8mL of 100mg/mL lead acetate solution, and fully stirring for 2 hours. The resulting dispersion was transferred to a 25ml Teflon reactor and allowed to react at 180 ℃ for 12 hours. And after the reaction kettle is cooled to room temperature, separating the graphene composite hydrogel obtained by the reaction through suction filtration, and washing with absolute ethyl alcohol and deionized water respectively.
(3) And (3) condensing the hydrogel obtained in the step (2) at-60 ℃ for 12 hours, and then, turning on a vacuum pump to freeze and dry for 24 hours to obtain the graphene composite aerogel.
(4) And (4) placing the graphene composite material aerogel obtained in the step (3) in a tubular furnace, continuously introducing argon, heating to 450 ℃ at the heating rate of 5 ℃/min, and calcining for 2h to decompose redundant organic structures in the composite material and completely convert lead into lead oxide. And after the calcination and sintering, continuously introducing argon until the temperature in the tube is reduced to room temperature, and finally obtaining the reduced graphene oxide/lead oxide composite material (marked as A-2).
(5) Using the graphene/lead oxide (A-2) (0.5 wt% relative to lead powder) obtained in the step (4) as a negative electrode additive to mix with lead powder (100 wt%), acetylene black (0.2 wt%), barium sulfate (0.83 wt%), humic acid (0.46 wt%), sodium lignosulfonate (0.4 wt%), short fibers (0.052 wt%), deionized water (12.5 wt%) and dilute sulfuric acid (7.9 wt%, 1.40g cm) -3 ) And uniformly mixing, coating on a lead grid, and curing to obtain the negative green plate of the lead-acid battery.
Example 3
(1) Weighing 100mg of lead acetate, and dissolving the lead acetate in 1mL of deionized water to obtain a 100mg/mL lead acetate solution; 56g of KOH powder was weighed into a 1L volumetric flask to prepare a 1mol/L KOH alkaline solution.
(2) Taking 10 ml of 1mg/ml graphene oxide dispersion liquid, wherein the solvent of the graphene oxide dispersion liquid is a mixed solvent of ethanol and water in a volume ratio of 1: 1. Weighing 200mg of aniline, adding the aniline into the graphene oxide dispersion liquid, magnetically stirring for 2 hours, dropwise adding 1mol/L KOH alkali solution into the mixed solution, stirring, adjusting the pH value to 10, and then weighing 1mL of 100mg/mL lead acetate solution into the mixed solution, and fully stirring for 2 hours. The resulting dispersion was transferred to a 25ml Teflon reactor and allowed to react at 180 ℃ for 24 hours. And after the reaction kettle is cooled to room temperature, separating the graphene composite hydrogel obtained by the reaction through suction filtration, and washing with absolute ethyl alcohol and deionized water respectively.
(3) And (3) condensing the hydrogel obtained in the step (2) at-60 ℃ for 12 hours, and then, turning on a vacuum pump to freeze and dry for 24 hours to obtain the graphene composite aerogel.
(4) And (4) placing the graphene composite material aerogel obtained in the step (3) in a tubular furnace, continuously introducing argon, heating to 450 ℃ at the heating rate of 5 ℃/min, and calcining for 2h to decompose redundant organic structures in the composite material and completely convert lead into lead oxide. And after the calcination and sintering, continuously introducing argon until the temperature in the tube is reduced to room temperature, and finally obtaining the reduced graphene oxide/lead oxide composite material (marked as A-3).
(5) Using the graphene/lead oxide (A-3) (0.5 wt% relative to lead powder) obtained in the step (4) as a negative electrode additive, mixing with lead powder (100 wt%), acetylene black (0.2 wt%), barium sulfate (0.83 wt%), humic acid (0.46 wt%), sodium lignosulfonate (0.4 wt%), short fibers (0.052 wt%), deionized water (12.5 wt%) and dilute sulfuric acid (7.9 wt%, 1.40g cm) -3 ) And uniformly mixing, coating on a lead grid, and curing to obtain the negative green plate of the lead-acid battery.
Example 4
(1) Weighing 100mg of lead acetate, and dissolving the lead acetate in 1mL of deionized water to obtain a 100mg/mL lead acetate solution; 56g of KOH powder was weighed into a 1L volumetric flask to prepare a 1mol/L KOH alkaline solution.
(2) Taking 10 ml of 1mg/ml graphene oxide dispersion liquid, wherein the solvent of the graphene oxide dispersion liquid is a mixed solvent of ethanol and water in a volume ratio of 1: 1. Weighing 100mg of aniline, adding the aniline into the graphene oxide dispersion liquid, magnetically stirring for 2 hours, dropwise adding 1mol/L KOH alkali solution, adding the KOH alkali solution into the mixed solution, stirring, adjusting the pH to 3, and weighing 1mL of 100mg/mL lead acetate solution, adding the lead acetate solution into the mixed solution, and fully stirring for 2 hours. The resulting dispersion was transferred to a 25ml Teflon reactor and allowed to react at 180 ℃ for 24 hours. And after the reaction kettle is cooled to room temperature, separating the graphene composite hydrogel obtained by the reaction through suction filtration, and washing with absolute ethyl alcohol and deionized water respectively.
(3) And (3) condensing the hydrogel obtained in the step (2) at-60 ℃ for 12 hours, and then, turning on a vacuum pump to freeze and dry for 24 hours to obtain the graphene composite aerogel.
(4) And (4) placing the graphene composite material aerogel obtained in the step (3) in a tubular furnace, continuously introducing argon, heating to 450 ℃ at the heating rate of 5 ℃/min, and calcining for 2h to decompose redundant organic structures in the composite material and completely convert lead into lead oxide. And after the calcination and sintering, continuously introducing argon until the temperature in the tube is reduced to room temperature, and finally obtaining the reduced graphene oxide/lead oxide composite material (marked as A-4).
(5) Using the graphene/lead oxide (A-4) (0.5 wt% relative to lead powder) obtained in the step (4) as a negative electrode additive, mixing with lead powder (100 wt%), acetylene black (0.2 wt%), barium sulfate (0.83 wt%), humic acid (0.46 wt%), sodium lignosulfonate (0.4 wt%), short fibers (0.052 wt%), deionized water (12.5 wt%) and dilute sulfuric acid (7.9 wt%, 1.40g cm) -3 ) And uniformly mixing, coating on a lead grid, and curing to obtain the negative green plate of the lead-acid battery.
Example 5
(1) Weighing 100mg of lead acetate, and dissolving the lead acetate in 1mL of deionized water to obtain 100mg/mL lead acetate solution; 56g of KOH powder was weighed into a 1L volumetric flask to prepare a 1mol/L KOH alkaline solution.
(2) Taking 10 ml of 1mg/ml graphene oxide dispersion liquid, wherein the solvent of the graphene oxide dispersion liquid is a mixed solvent of ethanol and water in a volume ratio of 1: 1. Weighing 150mg of aniline, adding the aniline into the graphene oxide dispersion liquid, magnetically stirring for 2 hours, dropwise adding 1mol/L KOH alkali solution, adding the solution into the mixed solution, stirring, adjusting the pH to 7, weighing 0.6mL of 100mg/mL lead acetate solution, and fully stirring for 2 hours. The resulting dispersion was transferred to a 25ml Teflon reactor and allowed to react at 180 ℃ for 36 hours. And after the reaction kettle is cooled to room temperature, separating the graphene composite hydrogel obtained by the reaction through suction filtration, and washing with absolute ethyl alcohol and deionized water respectively.
(3) And (3) condensing the hydrogel obtained in the step (2) at-60 ℃ for 12 hours, and then, turning on a vacuum pump to freeze and dry for 24 hours to obtain the graphene composite aerogel.
(4) And (4) placing the graphene composite material aerogel obtained in the step (3) in a tubular furnace, continuously introducing argon, heating to 450 ℃ at the heating rate of 5 ℃/min, and calcining for 2h to decompose redundant organic structures in the composite material and completely convert lead into lead oxide. And after the calcination and sintering, continuously introducing argon until the temperature in the tube is reduced to room temperature, and finally obtaining the reduced graphene oxide/lead oxide composite material (marked as A-5).
(5) Using the graphene/lead oxide (A-5) (0.5 wt% relative to lead powder) obtained in the step (4) as a negative electrode additive to mix with lead powder (100 wt%), acetylene black (0.2 wt%), barium sulfate (0.83 wt%), humic acid (0.46 wt%), sodium lignosulfonate (0.4 wt%), short fibers (0.052 wt%), deionized water (12.5 wt%) and dilute sulfuric acid (7.9 wt%, 1.40g cm) -3 ) And uniformly mixing, coating on a lead grid, and curing to obtain the negative green plate of the lead-acid battery.
Example 6
(1) Weighing 100mg of lead acetate, and dissolving the lead acetate in 1mL of deionized water to obtain a 100mg/mL lead acetate solution; 56g of KOH powder was weighed into a 1L volumetric flask to prepare a 1mol/L KOH alkaline solution.
(2) Taking 10 ml of 1mg/ml graphene oxide dispersion liquid, wherein the solvent of the graphene oxide dispersion liquid is a mixed solvent of ethanol and water in a volume ratio of 1: 1. Weighing 100mg of aniline, adding the aniline into the graphene oxide dispersion liquid, magnetically stirring for 2 hours, dropwise adding 1mol/L KOH alkali solution, adding the solution into the mixed solution, stirring, adjusting the pH to 3, weighing 0.6mL of 100mg/mL lead acetate solution, and fully stirring for 2 hours. The resulting dispersion was transferred to a 25ml Teflon reactor and allowed to react at 180 ℃ for 24 hours. And after the reaction kettle is cooled to room temperature, separating the graphene composite hydrogel obtained by the reaction through suction filtration, and washing with absolute ethyl alcohol and deionized water respectively.
(3) And (3) condensing the hydrogel obtained in the step (2) at-60 ℃ for 12 hours, and then, turning on a vacuum pump to freeze and dry for 24 hours to obtain the graphene composite aerogel.
(4) And (4) placing the graphene composite material aerogel obtained in the step (3) in a tubular furnace, continuously introducing argon, heating to 450 ℃ at the heating rate of 5 ℃/min, and calcining for 2h to decompose redundant organic structures in the composite material and completely convert lead into lead oxide. And after the calcination and sintering, continuously introducing argon until the temperature in the tube is reduced to room temperature, and finally obtaining the reduced graphene oxide/lead oxide composite material (marked as A-6).
(5) The graphene/lead oxide (A-6) (0.5 wt% with respect to the lead powder) obtained in step (4) was used as a negative electrode additiveThe agent is mixed with lead powder (100 wt%), acetylene black (0.2 wt%), barium sulfate (0.83 wt%), humic acid (0.46 wt%), sodium lignosulfonate (0.4 wt%), short fiber (0.052 wt%), deionized water (12.5 wt%) and dilute sulfuric acid (7.9 wt%, 1.40g cm -3 ) And uniformly mixing, coating on a lead grid, and curing to obtain the negative green plate of the lead-acid battery.
Comparative example 1
Comparative example 1 adopts the existing commonly used lead-acid battery lead plaster formula, that is, lead powder (100 wt%), acetylene black (0.2 wt%), barium sulfate (0.83 wt%), humic acid (0.46 wt%), sodium lignosulfonate (0.4 wt%), short fiber (0.052 wt%), deionized water (12.5 wt%) and dilute sulfuric acid (7.9 wt%, 1.40g cm-3) are mixed uniformly and then coated on a lead grid, and a lead-acid battery negative electrode green plate is obtained after curing, which is referred to as a blank comparative example hereinafter.
Comparative example 2
Comparative example 2 a common graphene processing method was used, a single-layer graphene commodity (0.5 wt%) purchased from hogfeng nano corporation was ground and mixed with micron-sized lead powder (2.5 wt%), and in the negative electrode and paste process, the single-layer graphene commodity was uniformly mixed with lead powder (100 wt%), acetylene black (0.2 wt%), barium sulfate (0.83 wt%), humic acid (0.46 wt%), sodium lignosulfonate (0.4 wt%), short fibers (0.052 wt%), deionized water (12.5 wt%) and dilute sulfuric acid (7.9 wt%, 1.40g · cm-3), and then the mixture was coated on a lead grid, and the lead-acid battery negative electrode green plate was obtained after curing, which is referred to as a common comparative example hereinafter.
Comparative example 3
A reduced graphene oxide sample was prepared by a hydrothermal method with reference to the operations of steps (1) to (4) in example 1 except that aniline and lead acetate were not added. A Scanning Electron Microscope (SEM) photograph of the sample material is shown in fig. 1.
Comparative example 4
A reduced graphene oxide sample was prepared by a hydrothermal method with reference to the operations of steps (1) to (4) in example 1, except that lead acetate was not added. A Scanning Electron Microscope (SEM) photograph of the sample material is shown in fig. 2.
Comparative example 5
A reduced graphene oxide sample was prepared by a hydrothermal method with reference to the operations of steps (1) to (4) in example 1 except that aniline was not added. A Scanning Electron Microscope (SEM) photograph of the sample material is shown in fig. 3.
Effects of the implementation
The results from fig. 1-4 using Scanning Electron Microscopy (SEM) testing show that reduced graphene oxide sheets without added aniline and lead acetate show smooth wrinkles, no particulate matter attached, and thicker stacking between sheets; the reduced graphene oxide sheet layer without adding lead acetate is seriously folded, has more folds and unsmooth surface; the surface of the graphene oxide sheets without aniline is smooth, and the graphene oxide sheets have irregular blocky lead oxide with larger size and are distributed unevenly; the surface of the A-1 sample prepared in the embodiment 1 is uniformly loaded with lead oxide particles with the diameter of about 200nm, and the nano lead oxide among the sheets can effectively inhibit the stacking of graphene sheets to form an effective three-dimensional structure, so that not only are abundant reaction active sites provided, but also an effective ion diffusion path is formed.
FIG. 5 is a Transmission Electron Microscope (TEM) spectrum and an EDS composition analysis of the A-1 sample, from which the microstructure of the graphene sheets uniformly loaded with nanoscale lead oxide can be confirmed again.
Fig. 6 to 7 show that the negative electrode green sheets prepared in examples 1 to 6, the blank comparative example and the conventional comparative example are assembled with the positive electrode sheet of the lead-acid battery to form a flooded battery, and the cycle life and the specific capacity of the high-rate partial charge operating condition (HRSoC) are measured and compared (detailed data can be seen in table 1 below). After the graphene additive is introduced by using a conventional method, the cycle performance and specific capacity of the lead-carbon battery are obviously improved compared with those of the traditional lead-acid battery, and the lead-carbon battery added with the additive prepared by the invention is further improved in the aspects of HRPSoC cycle life and specific capacity.
FIG. 8 is a comparative graph showing hydrogen evolution performance of the negative electrode green sheets obtained in example 1, the blank comparative example and the conventional comparative example. It can be seen from the figure that the hydrogen evolution overpotential of the blank comparative example without adding the graphene material is the highest, while the hydrogen evolution overpotential of the common comparative example with adding the graphene material according to the common method is the lowest, which is indistinguishable from the influence caused by the lower hydrogen evolution overpotential of the carbon material itself. However, after the reduced graphene oxide/lead oxide additive prepared in embodiment 1 of the present invention is added, the hydrogen evolution overpotential of the negative plate is substantially the same as that of the blank comparative example without adding graphene, which proves that the present invention can effectively inhibit hydrogen evolution, and has a significant effect on slowing down water loss failure of the battery.
The performance indexes of the flooded lead-acid storage battery assembled by the negative green plates prepared by the implementation examples 1-6, the blank comparative example and the common comparative example are detected, and the results are shown in table 1.
As can be seen from table 1, the lead-acid battery using the additive containing reduced graphene oxide/lead oxide composite material prepared by the present invention has better cycle life and specific capacity, the cycle life is increased by more than 100%, and the specific capacity is also increased by more than 10% compared with the lead-acid battery using the existing conventional method to add graphene in the conventional comparative example; compared with a lead-acid battery without graphene in a blank comparative example, the cycle life and the specific capacity are remarkably improved, the cycle life is improved by more than 300%, and the specific capacity is improved by more than 24%. The invention can greatly improve the cycle life and specific capacity of the common lead-acid battery, and can reflect the capability of solving the problems of floating carbon, hydrogen evolution, potential matching and the like when the graphene is used as the negative electrode additive of the lead-carbon battery by a common method to a certain extent.
TABLE 1
It should be noted that the above-mentioned embodiments are only for illustrating the present invention and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Claims (10)
1. A preparation method of a reduced graphene oxide loaded lead oxide composite material for a lead-carbon battery is characterized by comprising the following steps:
(1) fully mixing the graphene oxide dispersion liquid with aniline and lead acetate solution, and then adding the mixture into a reaction kettle to perform hydrothermal reaction; in the reaction raw materials, the mass ratio of the graphene oxide to the aniline to the lead acetate is 1: 5-20: 6-10;
(2) separating the graphene/lead composite hydrogel in the reaction product, and washing with absolute ethyl alcohol and deionized water; then carrying out condensation treatment and freeze drying to obtain reduced graphene oxide/lead oxide composite material aerogel;
(3) and calcining the reduced graphene oxide/lead oxide composite aerogel under the protection of argon to obtain the reduced graphene oxide loaded lead oxide composite.
2. The method according to claim 1, wherein in the step (1), before hydrothermal reaction:
(1.1) adding lead acetate (Pb (CH) 3 COO) 2 ·3H 2 O) dissolving in deionized water to obtain a lead acetate solution;
(1.2) adding aniline into the graphene oxide dispersion liquid, magnetically stirring for 2 hours, and adding an alkali solution to adjust the pH value to 3-10; and adding a lead acetate solution into the mixture, continuously stirring the mixture for 2 hours, and using the obtained mixed solution for hydrothermal reaction.
3. The method of claim 2, wherein the base solution is obtained by dissolving KOH in deionized water.
4. The method according to claim 2, wherein the solvent of the graphene oxide dispersion is a mixed solvent of ethanol and water in a volume ratio of 1: 1.
5. The method according to claim 2, wherein the concentrations of the lead acetate solution, the alkali solution and the graphene oxide dispersion solution are 100mg/mL, 1mol/L and 1mg/mL, respectively.
6. The method according to claim 1, wherein in the step (1), the hydrothermal reaction is carried out at 180 ℃ for 12-36 hours.
7. The method according to claim 1, wherein in the step (2), the temperatures of the condensation treatment and the freeze drying are both-60 ℃; wherein the time for the condensation treatment was 12 hours, and the time for the freeze-drying was 24 hours.
8. The method according to claim 1, wherein in the step (2), the freeze-drying is performed under vacuum.
9. The method according to claim 1, wherein in the step (3), the calcination temperature is 450 ℃, the calcination time is 2 hours, and the temperature rise rate during the calcination is 5 ℃/min.
10. The application method of the reduced graphene oxide loaded lead oxide composite material obtained by the method in any one of claims 1 to 9 is characterized in that the composite material is used as a negative electrode additive, is uniformly mixed with lead powder, acetylene black, barium sulfate, humic acid, sodium lignosulfonate, short fibers, deionized water and dilute sulfuric acid, is coated on a lead grid, and is solidified to obtain a lead-acid battery negative electrode green plate.
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